Silver halide-containing photographic material

ABSTRACT

A photographic light-sensitive material having a silver halidecontaining photosensitive emulsion layer on its surface is effectively rendered non-adherent or non-tacking by providing on at least one surface thereof a non-photosensitive layer containing a polymer having as its recurring unit a monoester of an aliphatic polyhydric alocohol with acrylic acid or methacrylic acid.

United States Patent [191 Usami et al.

1451 Oct. 8, 1974 1 SILVER HALIDE-CONTAINING PHOTOGRAPHIC MATERIAL [75] Inventors: Toshimasa Usami; lkutaro Horie;

Kunio lshigaki; Takushi Miyazako; Shinii Sakaguchi, all of Kanagawa,

Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: June 15, 1973 [21] Appl. No.: 370,571

[30] Foreign Application Priority Data June 15, 1972 Japan 47-59743 52 us. Cl. 96/67, 96/87 R, 96/94 R 51 Int. Cl G036 1/02 [58] 9 Field of Search 96/67, 94 R, 71, 28, 83, 96/84 R, 87 R [56] 7 References Cited UNITED STATES PATENTS 2,772,166 11/1956 Fowler, Jr 96/114 3,105,762 10/1963 Byrhe et a]. 96/67 Primary Examiner-David Klein Assistant Examiner-Alfonso T. Suro Pico Attorney, Agent, or Firm-Sughrue, Ro'thwell, Mion, Zinn & Macpeak 57 ABSTRACT 17 Claims, No Drawings SILVER HALIDE-CONTAINING PHOTOGRAPHIC MATERIAL BACKGROUND OF THE INVENTION When a photosensitive material produced under such severe conditions is fiu t iii ahigh teinperature and high humidity atmosphere, the surface thereof becomes much more cohesive or adherent than one obtained under milder coating and drying conditions, which results in various defects such as it adheres to the back side of the support and also to other surfaces with which it closely contacts.

Such a difficulty takes place much more frequently and becomes more serious as the fields of use of photosensitive materials expand.

In order to resolve this problem, it has been proposed and widely known to those skilled in the art that the sticking tendency of a photosensitive material can be reduced to a certain extent by admixing with its surface coating layer globular particles of polymethyl methacrylate or colloidal silica particles, to thereby increase surface coarseness. However, these known methods often invite various other disadvantages including a loss of film transparency, impairment of smooth running of the film inside a camera, a reduction of granularity in the picture image, etc., so that the amount of such additives added is confined to a minimum level, which in turn gives less effect for obtaining the desired result.

The use of certain types of surface active agents has been considered, but this proposal has not yet been put into practice for photographic materials for the reason that most of them cause problems upon coating, impair photographic characteristics and result in undesirable formation of precipitates due to dissolution into a developing liquid.

This sticking problem also becomes serious in producing muIti-layered color film because the film is coated several times with various photographic emulsions, and the intermediate product film is stacked in the form of a roll after it has completed the first coating operation, when strong adhesion takes place between the coated surface and the back side of the support.

SUMMARY OF THE INVENTION The object of this invention is to provide a photographic light-sensitive material which is not sticky or adherant without substantially impairing its inherent photographic characteristics or causing objectionable side-effect during manufacture.

This object has been accomplished by introducing on the surface layer of a photographic silver halide lightsensitive material a polymer containing as recurring units a monoester of an alipathic polyhydric alcohol withacrylic acid or methacrylic acid. 7

According to this invention, a photographic material having at least one silver halide photosensitive emulsion layer on a support can be rendered non-sticky or non-adhesive by admixing with the non-photosensitive surface layer of the photographic material a homopolymer or copolymer of at least one monoester of an aliphatic polyhydric alcohol with either acrylic acid or methacrylic acid.

DETAILED DESCRIPTION OF THE INVENTION The term non-photosensitive surface layer used herein includes a non-photosensitive surface layer which is provided on the emulsion layer side of the photographic light-sensitive material and a nonphotosensitive outer layer which is provided on the surface of the opposite side of the emulsion layer. As a practical example, it includes a protective coating layer and a back coating layer of a photographic lightsensitive material, an intermediate layer, filter layer or like non-photosensitive layers of an intermediate product.

The polymer used in this invention, i.e., that contains as its recurring unit a monoester of an aliphatic polyhydric alcohol with acrylic acid or methacrylic acid, includes, for example, homopolymers, copolymers or graft copolymers of monomethacrylic acid esters or monoacrylic acid esters of an aliphatic polyhydric alcohol. Examples of such esters are 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2- hydroxypropyl methacrylate, '4-hydroxybutyl methacrylate, S-hydroxypentyl methacrylate, 2,2-dimethyl-3- hydroxypropyl methacrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydro'xybutyl acrylate,S-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, diethylene glycol monoacrylate, trimethyl-olpropane monoacrylate and pentaerythritol monoacrylate, and the like.

Preferred aliphatic polyhydric alcohols include those containing from 2 to 5 hydroxy gro ups and from 2 to about carbon atoms. y

The comonomers constituting other monomers to be copolyme'rized with the above monoesters can be any of the well known olefinic polymerizable monomers including the vinylic monomers and the diolefmic monomers. Thus, for example, the vinylic monomers can include styrene or substituted styrenes, acrylic acid esters, methacrylic acid esters, vinyl ethers, vinyl ketones, vinylidene chloride, vinyl chloride, vinyl esters, acrylonitrile, substituted acrylonitriles, vinyl pyridines, acrylamides, allylamines, and similar well known vinylic monomers. Similarly, the polymerizable diolefms such as l,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-l ,3-butadiene and similar diolefinic monomers are suitable for use in practicing the invention. I

Typical monomers, which can be employed in practicing the invention include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl' acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decylacrylate, B-cyanoethyl acrylate, B-chloroethyl acrylate, n-butyl acrylate,

3. 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- butoxyethyl acrylate, and similar alkyl acrylates wherein the alkyl group contains from 1 to 12 carbon atoms; methacrylates containing from l to 12 carbon atoms in the alkyl group, such as n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, noctyl methacrylate, ethyl methacrylate, methyl methacrylate and the like; styrene monomers such as styrene or a substituted styrene such as o-methyl styrene. mmethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3,5- dimethyl styrene, 2,4,5-trimethyl styrene, 2,4,6- trimethyl styrene, 2,4,5-triethylstyrene, o-ethylstyrene, n-ethylstyrene, p-ethylstyrene, 3,5-diethyl styrene, p-nbutyl styrene, m-sec-butyl styrene, m-tert-butyl styrene, p-hexyl styrene, pn-heptyl styrene, p-2- ethylhexyl styrene, o-fluoro styrene, m-fluoro styrene, p-fluoro styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene 2,3-dichloro styrene, 2,4-dichloro styrene, 2,5-dichloro styrene 2,6-dichloro styrene, 3,4- dichloro styrene, 3,5-dichloro styrene, 2,3,4,5,6- pentachloro styrene, m-trifluoromethyl styrene, ocyano styrene, m-cyano styrene, m-nitro styprene, pnitro styrene, p-dimethyl amino styrene, Z-methyl styrene and similar styrene derivatives; acrylonitrile monomers such as scrylonitrile or a substituted acrylonitrile such as methacrylonitrile, a-chloroacrylonitrile, oz-bromoacrylonitrile, trifluoromethyl acrylonitrile, a-trifluoromethylcarboxy acrylonitrile, and the like; vinyl esters such as vinyl acetate, vin'ylpropionate, vinyl butyrate, or the like; vinyl pyridines' such as 4- vinyl pyridine, Z-methyl-S-vinyl pyridine and the like;

vinyl ketones such as methylvinyl ketone, ethylvinyl ke tone, and the like; vinyl ethers such as methylvinyl ether and the like; alkenyl esters such as isopropenyl acetate and the like, and similar well known polymerizable unsaturated monomers such as acrylic acid, allylamine, methacrylic acid, acrylamide, methacrylamide, N-alkyl acrylamides and N-alkyl methacrylamides containing from 1 to 12 carbon atoms in the alkyl group such as N-methyl acrylamede and N-methyl methacrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-methylol acrylamide, N-hydroxyethyl acrylamide, N-tert-butyl acrylamide, N-cyclohexyl acrylamide, diaceton-acrylamide, N-(1,l-dimethyl-3-hydroxybutyl) acrylamide, N-(B-morpholino) ethyl acrylamide, N- allyl acrylamide, N-benzyl acrylamide, N-acryloyl morpholine, N-methacryloyl morpholine, N-methyl-N- acryloyl piperazine, N-acryloyl piperazine, N-acryloyl pyrrolizine, N-acryloyl hexamethyleneimine and the like, diacrylates or dimethacrylates of an aliphatic poly hydroxy alcohol hereinbefore described, and maleic anhydride, itaconic acid, vinyl imidazole, vinyl oxazolinone, vinyl pyrrolidone, and the like.

The ratio ofmonomers in the copolymerization is not critical, but the proportion of monomethacrylate or monoacrylate of the aliphatic polyhydric alcohol in the copolymer is desirably in excess of 50 mol prefera-- bly more than about 60%. The comonomer can be used as a combination of two or more thereof.

The molecular weight of the homopolymer or copolymer may be in general greater than 10,000, preferably about 50,000 to 500,000, which, however, is not critical.

The graft polymers used in the present invention include polymers in which one or more monomers described above are grafted onto a parent polymer.

The parent or base polymer of the graft copolymer used in the present invention is a hydrophilic polymeric material containing a functional group having active hydrogen such as an amino, imino, etc., group onto which the polymerizable monomer of the above described esters is grafted, with or without another copolymerizable monomer as described above. Suitable parent polymers include gelatin, acylated gelatin, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, starch, hydroxyethyl cellulose and the like. As acylated gelatins there can be employed the reaction product of gelatin with an organic acid anhydride or a chloride such as succinyl gelatin, phthalyl gelatin or acetyl gelatin. Such acylated gelatin is well known in the art, and the preparation thereof is described, e.g., in U.S. Pat. Nos. 2,525,753 and 2,691,582.

The amount of the monomer or monomers grafted ranges from about 5 to 95% by weight of the total amount of starting materials subjected to reaction, with a preferred range being 10 to 60% by weight.

Among the monomers, it is desirable that at least 50% thereof be the monomethacrylate and/or methacrylate of the aliphatic'polyhydric alcohol and the ester should be contained in an amount of at least 5% of the total amount of starting materials. Forexample, if the ratio of monomer is 5% (lower limit), all should be the ester, while'if its 6%, 5% is ester and 1% can be another monomer.

The method of polymerization by which the polymer of thisinvention is prepared is not limited to any particular one and involves conventional solution polymerization process, graft-polymerization proceses, etc.

The process for the synthesis of the polymer will be explained in more detail hereinbelow, but it should not be considered to be limited, thereto. For example, the polymers can be prepared'according to the method described in British Patent 1,211,039. Synthesis Example 1 Synthesis of poly-2-hydroxyethyl methacrylate To a solvent mixture comprising 550 ml. of water and I 550 ml. of ethanol were added 200g of 2-hydroxyethyl methacrylate, lg of potassium persulfate and lg of sodium hydrogen sulfite. The resultant mixture was stirred for 4 hours at 60C under a nitrogen atmosphere. After filtering, the reaction product obtained as the filtrate was poured into 11 liters of water and the precipitate formed was collected and dried under vacuum to give the indicated polymer having a molecular weight of approximately 350,000 in' a yield of g. Synthesis Example 2 Synthesis of a copolymer of 2-hydroxyethyl methacryl ate and acrylamide To a solvent mixture comprising 550 ml. of water and l 550 ml. of ethanol were added 176g of 2-hydroxyethyl hydroxypropyl methacrylate and lg of azobisisobutyronitrile. The resultant mixture was continuously stirred at 70C for 3% hours. The thus reacted solution was then filtered and the filtrate was poured into 12 liters of water to precipitate the polymer which was there-after dried under vacuum. The indicated copolymer having a molecular weight of approximately 570,000 was obtained in a yield of 260g. Synthesis Example 4 Synthesis of the copolymer of 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate According to the procedure of Synthesis Example 2, 94g of 2-hydroxyethyl acrylate and 106g of 2- hydroxyethyl methacrylate were copolymerized to give the indicated copolymer having a molecular weight of approximately 230,000 in a yield of 186g. Synthesis Example 5 Synthesis of the copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate To a solvent mixture comprising 500 ml. of water and 1500 ml. of' methanol were added 419g of 2- hydroxyethyl methacrylate, 81g of methyl methacrylate and 1.5g of benzoyl perioxide. The resultant mixture was continuously stirred at 60C for 4 /2 hours under a nitrogen atmosphere. The resultantproduct was treated as in Synthesis Example 3 to give the indicated copolymerhaving a molecular weight of approximately 480,000 in a yield of 430g. Synthesis Example 6 Synthesis of the graft-copolymer of hydroxyethyl cellulose with 2-hydroxy diethyl methacrylate To a solvent mixture comprising 750 ml. of water and 150 ml. of ethanol was added 50g of hydroxyethyl cellulose (molecular weight of about 150,000) and dissolved at 60C. After flushing the system with nitrogen, the solution was further heated to a temperature of 75C, and thereafter 50g of 2-hydroxyethyl methacrylate containing 0.3g of benzoyl peroxide was added dropwise thereto from a dropping funnel under stirring for 4 hours. Reaction was under a nitrogen gas atmosphere. The reaction product was put in a dialysis film and subjected to dialysis for 20 hours by immersion in flowing water, and then freeze-dried to give the indicated copolymer in a yield of 88g.

Synthesis Example 7 Synthesis of the graft-copolymer of gelatin with 2- hydroxyethyl methacrylate Twenty grams of photographic grade gelatin was dissolved at 60C in 100 ml. of a glycerin/water (1:1 by volume) mixture. 300 ml. of an ethanol/water (3:1 by volume) mixture was added slowly thereto, after which 20g of 2-hydroxyethyl methacrylate and lg of benzoyl peroxide were added over about 10 minutes. The resultant mixture was heated at 80C for 2 hours to effect polymerization. After cooling the reacted mixture to 60C and allowing it to stand for 20 minutes, the reacted mixture was poured into water to obtain a fibrous precipitate which was washed with water and dried to give the indicated graft-copolymer.

1n the Synthesis Examples the reaction was carried out under atmospheric pressure. The pressure is not critical.

In order to prepare a coating solution of the polymer of this inventionpvarious solvents may be used to dissolve the polymer. Examples of such solvents include water, methanol, ethanol, propanol, butanol, glycols,

methyl cellusolve, etc. These solvents may be used, if desired, as a combination of two or more thereof.

The polymer-containing coating solution may contain, if desired, a hydrophilic high molecular weight substance as is commonly used as a hydrophilic colloid or binder in the field of silver halide photographic materials, such as gelatin, gelatin derivatives, e.g., acylated gelatin such as those described hereinbefore as to the parent polymer, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, et'c., polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, starch, etc.

The coating solution may further contain other additives conventionally usedin the art, for example, a hardening agent such as an aldehyde hardening agent. a methylol hardening agent. a 1,4-dioxane hardening agent, an axiridine hardening agent, an iso-oxazole hardening agent, a carbodiimide hardening agent, an active halogen hardening agent or an active vinyl hardening agent (typical examples of such hardening agents are described in U.S. Pat. Nos. 3,232,764; 3,288,775;

3,321,313 and 3,543,292 and British Patents Nos. 974,723; 1,167,207 and 994,869), a vinyl polymer latex as described in U.S. Pat. Nos. 2,376,005; 2,772,166 and 2,853,457, a hydroquinone derivative as described in U.S.: Pat. Nos. 2,336,327; 2,360,290; 2,403,721; 2,418,613; 2,704,713; 2,728,659; 2,732,300 and 2,735,765, 'a coating aid such as an anionic, cationic, nonionic or'ampholitic surface active agent, a surface-roughening agent or matting agent such as silica, strontium barium sulfate, etc., an antistatic agent and the like.

The coating solution containing the. above polymer may be applied to the surface of the silver halidecontaining photo-sensitive material according to any known manner which has heretofore been employed in the production of photographic materials. Such coating methods include, for instance, dip coating, air-knife coating, curtain coating,extrusion coating and a simultaneous multi-layer coating process as described in U.S. Pat. Nos. 2,761,791 and 3,526,528 and British Patent No. 837,095.

The support material'used in this invention to which the silver halide-containingphotographic emulsion is applied can be any of those knownin the art and is exemplified by cellulose esters, polyvinyl acetal, polyethylene terephthalate,polystyrene, baryta paper, polyethylene laminated paper, synthetic paper, etc.

The silver halide-containing emulsion used in the photographic emulsion(s) of this invention contain, as a silver halide, for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochlorobromide and like crystalline mixtures of two or more thereof, which are conventionally prepared and optionally chemically sensitized according to widely known methods.

The above emulsion can be a single or multicomponent vmixture. While photographic additives other than the' above are not necessary,-in commercial practice materiale as arecommonly used in the artto improve the ease of coating, storability or handling characteristics of the emulsion will commonly be added to in an amount as is used by the art, for example, such as a spectral sensitizer, stabilizer, fog inhibitor, color coupler, polyalkylene oxide, gelatin plasticizer, vinyl polymerlatex, hardener, coating aid, etc. Needless to say, these components are not mandatory and the present invention should not be construed as requiring the presence of such components, though practically speaking theywill generally be used in commercial size operations.

As a binder for the photosensitive emulsion layer, the use of gelatin as a main component is generally preferred. However, the emulsion layer may contain other materials such as gelatin derivatives such as acylated gelatin described hereinbefore as to the parent polymer, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, etc., polysaccharide,-synthetic high molecular weight substance (e.g., polyvinyl alcohol, poyvinyl pyrrolidone), and thelike.

Since the photosensitive material of this invention is characterized by having at least one surface layer formed of or containing at least one of the above polymers, it is possible, of course, to add and use any other known components or any other conventional techniques without departing from the essential spirit of this invention.

Adhering or sticking problems which previously unavoidably took place whenever the coated surface layer is put together in tight contact with other surfaces under an atmosphere of high humidity, e.g under a relative humidity as high or more than 65%, have now been obviated to a great extent in accordance with this invention, in which the surface layer of a photographic material is provided with a coating layer consisting of or containing the above-described polymer.

The surface treatment of this invention using the above polymer can be combined, if desired,-with any other known stickiness-reducing treatment which has been proposed up to now, e.g., a surface-coarsening process and the addition of a specific type of. surface active agent as described previously. In this case, a corresponding additional effect is generally obtained.

The non-photosensitive layer containing the specific polymer of this invention exhibits a superior stickproofing or non-tacky property whenever it is formed on a complete product or on an intermediate product, and effectively prevents the photographic materials during their production or handling from problems invited by the adhesive or tacky surface thereof.

In light of the above discussion, it should be clear to one skilled in the art that the protective layer of the present invention is, essentially speaking, either the topmost layer on the emulsion side of the film and/or the topmost layer on the rear side of the film, in a final product. When used for an intermediate product, generally the protective layer will be anintermediate layer in the final product. Therefore, inorder to secure a low adhesion surface in a final product, it will be obvious the surface layer in the final product must contain the polymer. The use in an intermediatelayer per se is not, however, excluded from the present invention where the main adhesion problem is encountered with the intermediate product.

From the above discussion, it will be clear that the amount of polymer in accordance with the present invention which provides the affect of lowering adhesiveness or tackiness can vary greatly. However, in practical usage it is generally desirable that in any layer'containing the polymer at least about 10% by weight of the layer be the polymer of the present invention, and 20% above range applies primiarily to cases of mixtures of the polymers of this invention with, for example, a different hydrophilie high molecular weight substance.

The thickness of the layer containing the polymer of the invention is less important than the-proportion of the polymer present. Generally speaking, however, considering the handling of photographic elements and the fact they are sometimes subjected to rough handling, itis preferred that the minimum thickness of the layer containing the polymer of the present invention, be it present alone or in mixture form with another substance, be about O.3 micron, and it is more preferred that the thickness be at least 0.5 micron. No significant improvement is obtained by'using a layer greater than 3 microns thick, and accordingly it is particularly pre: ferred to use a layer of from 0.5 to 3 microns in thickness.

Theinvention will now be illustrated in further detail by the following specific examples In the examples, all percentages are by weight unless otherwise indicated.

- EXAMPLE 1 g The :lOOOg of a gelatin-based silveriodob'rom'idephotographic emulsion containing mol silver iodide (the emulsion comprised 10% silver halide, 6% gelatin and 84% water),"there were added g'of a 0.1% methanolsoluti on of a spectral sensitize'rhaving the following formula, I g

50g of a' 1% aqueous solution of 5-methyl-7-hydroxy- 2,3,4-triazaindolidine, 450g of a cyanine coupler dispersion having the following composition and 30g of a 2% aqueous solution of 2,4-dichloro-6-hydroxy-S- triazine sodium salt.

Cyanine Coupler Dispersion:

queous gelatin solution (i070) lOOOg Aqueous sodium dodecylhenzene 80g sulfonate solution (5%) Cyanine coupler 80g Butyl acetate 50g ibutyl phthalate. g

(yunine coupler having the following formula 0 ONHCmHu dried thickness of 1.5 ,u. to thereby prepare test films A and B, respectively.

Coating solution A:

Prepared according to Synthesis Example I The thus prepared test films A and B were each cut into fragments each having an area ofa square cm on a side, each surface of which was brought into tight contact with the rear face of a cellulose triacetate base while imposing a pressing load of 3 Kg and allowed to stand under a relative humidity (RH) of 85% at a temperature of 40C over a period of 3 days and 6 days. Thereafter, the pressed film was stripped from the cellulose triacetate base, and the condition of the film sur- I face was examined. The surface of the film which had been closely attached to the base by being tightly contacted and adhered thereto had a rather smooth and glossy appearance to such an extent that it could not be clearly distinguished from other parts where no tight adhesion took place. The proportion of such glossy area to the total surface area in'percent was taken to evaluate the effectiveness of the top coating of this invention containing the specific polymer. The results are given in Table 1 below.

The tendency of surface tackiness or adhesiveness can be conveniently evaluated by comparing the size of the glossy area, i.e., the larger the percent of glossy area the greater the adhesion.

As is apparent from the results of Table l, film B of this invention which is a photosensitive material having a surface layercontaining poly-Z-hydroxyethyl methacrylate has a more reduced surface tackiness than film A prepared according to a known method.

This type of film is usually formed as an intermediate product during the course of manufacturing multilayered color photographic materials, so that adherance problems which often take place during the hairdling thereof can be efficiently overcome by providing a surface layer containing a specific polymer of this invention, as seen in the case of test film B.

EXAMPLE 2 Test film A prepared in Example 1 was coated in a 6 LII that used in Example I as the red-sensitive-layer with 150g of a 0.1% methanol solution of a spectral sensitizer represented by the following formula 2H5 iHa 50g of a 1% aqueous solution of 5-methyl-7-hydroxy- 2,3,4-triazaindolidine, 600g of a magneta coupler dispersion having the following recipe and 20g of a 2% aqueous solution of 2,4-dichloro-6-hydroxy-S-triazine sodium salt. Thus, a green sensitive emulsion layer was formed.

Magenta coupler dispersion Aqueous gelatin solution (10%) lOOOg Aqueous sodium dodecylbenzene sulfonate solution (5%) g Magenta coupler 100g Ethyl acetate 200g ibutyl phthalate l20g Magenta coupler having the following chemical formula:

Onto the resultant film, a 5% aqueous gelatin solution containing yellow colloidal silver was applied in a dried thickness of l'.5 u so as to form a yellow filter layer.

Next, a blue-sensitive emulsion layer was formed by coating the resultant film with a layer of a dried thickness of 6 p. with a coating liquid prepared by adding to l000g of a gelatin-based silver iodobromide photographic emulsion [containing 6 mol silver iodide (comprising 10% silver-halide, 12% gelatin and 78% water); having an average particle diameter of 1.2 ,u] 20g of a 1% aqueous solution of 5-methyl-7-hydroxy- 2,3,4-triazaindolidine, 500g of a yellow coupler dispersion having the following recipe and 20g of a 2% aqueous solution of 2,4-dichloro-6-hydroxy-S-triazine sodium salt.

Yellow coupler dispersion:

queous gelatin solution (5%) lOOOg Aqueous solution of sodium dodecyl benzene sulfonate (5%) lOOg Yellow coupler 200g Ethyl acetate 100g ricesyl phosphate 100g Yellow coupler having the formula below NHC OCHa-O moo-Q-o cm 0 0 NEG The film thus obtained was divided into three parts which were then coated in a dried thickness of L5 1 with one of protective coating solutions C, D and E having the following recipes, respectively, to'form test films C, D and E.

Coatingsolution C Test films C, D and E were each' subjected to a sticking test in the same manner as employed in Example 1.

tHii

The rcsultsare given in Table 2 below. Test film Dhaving the surface layer according to this invention exhibited a remarkably improved resistance to-sticking or lack of adhesiveness as compared to test films C and D which had been coated with a liquid containing no specific polymer. 1

Table 2 Glossy Area (7r) Film After 3 days storage After 6 days storage C Approx. 20 Approx. 60 D 0 Approx. 20 E Approx. 15 Approx. 70

EXAMPLE 3 I A conventionally undercoated polyethylene terephthalate base was coated to a dried thickness of 10 1.4. with a coating solution prepared by admixing 1000g of the same silver halide emulsion .used in the blue C5Hu Film Composition V F Bone gelatin G Poly(2-hydroxyethyl methacrylate/hydroxyethyl acrylatc)* Bone gelatin containing 5% of globular particles of polymothyl methacrylatc(average particle size of 2 p.) v

l Polyacrylamidc J Bone gelatin (50%) Polyacrylamide (50%) Prepared by Synthesis Example 4 Each of the test films was closely attached to the rear sideof the polyethylene terephthalate base and stored for 5 days and 10 days under the same conditions as employed in Example 1 to determine its tendency to stick. The results are shown in Table 3.

Table 3 Glossy area Film After 5 days storage After 10 days storage F Approx. 10 Approx. 40 G 0 do. 5 H O do. l()

l Approx. 10 do. 50 .I do. 10 do. 40

Test film G having a surface layer according to this invention exhibited an excellent antirsticking property compared to known films F, H, l and J.'After developing these films, film l-l lost its original transparency, whereas film G of this invention remained transparent.

EXAMPLE 4 g A conventionally undercoated cellulose triacetate base was coated to a dried thickness of 14 p. with a coating liquid prepared by mixing 1000g of a gelatinbase silver iodobromide photographic emulsion [comprising 7% silver halide, 6% gelatin and 87% water; containing 5 mol silver iodide and having an average particle size of 0.70 ,u] with 5g of a 0.1% methanol solution of l,l-diethyl-2,2-cyanine chloride, 40g of a 0.1% methanol solution of 3,3-diethyl-9-methylthiacarbocyanine bromide, 50g of a 1% aqueous solution of 5-methyl-7-hydroxy-2,3,4-triazaindolidine, 400g of a polyethyl acrylate latex having a particle size of 0.2 a, 5g ofa 5% aqueous solution of sodium lauryl sulfate and 20g of a 2% aqueous solution of 2,4- dichloro-6-hydroxy-S-triazine sodium salt.

* Composition of polyacrylate latex Polyethyl acrylate 20% Sodium lauryl sulfate 2% Water 78% (trace amount of henzoyl peroxide as a polymerisation initiator was present) The resultant film was further provided with a protective layer of various compositions as shown below to Film Composition Bone gelatin L Poly(2-hydroxyethylmethacrylate/methyl methacrylate) (prepared according to Synthesis Example 5) Graft-copolymer of hydroxyethyl cellulose with Z-hydroxyethyl methacrylate (prepared according to Synthesis Example 6) Table 4 Glossy Area (70) Film After 3 days storage After 6 days storage K 7 Approx. 40 Approx. 80 L 0 do. 10 M Approx. 5 do. l0

AMP 5 Using the same silver halide emulsion as employed in Example 3, a conventionally undercoated cellulose triacetate base was coated with protective coating liquid N or P according to the simultaneous twot-layer coating.

7 method as disclosed in US. Pat. No. 3,526,528 at various drying rates to prepare films N-l to N3 and P-l to P-3, respectively.

Coatin solution N Aqueous bone gelatin solution (5%) l000g Aqueous sodium dodecylbenzene sulfonate solution (5%) g Aqueous solution of 2,4-dichloro-6- hydroxyS-triazine sodium salt (2%) 20g Coatin solution P Aqueous hone gelatin solution (571) 600g Solution of poly-Z-hydroxyethyl methacrylate* in ethanol/water (20/80) (5%) 400g Aqueous sodium dodecylhcnzenc sulfonate solution (5'71) 20g Aqueous solution of 2,4-dichloro fthydroxy-S-triazine sodium salt (2%) 20g Prepared according to Synthesis Example I Each film was subjected to the adhering test used in Example 1 to give the results shown in Table 5. In Table 5 the dry thickness of the protective layer was l.5 microns.

Table 5 It will be noted from the above results that the photographic material having the' surface layer containing poly-Z-hydroxyethyl methacrylate according to this in-. vention exhibits a superior anti-sticking property even if it has not been subjected to high speed drying.

EXAMPLE 6 The surface of a biaxially stretched, crystallized polyethylene terephthalate film was coated with a solution having the following recipe and dried at 120C for 10 minutes to provide a back layer of a dried film thick ness of 0.5 a, which was called film Q.

ethylene glycol I do. trimethylene glycol l do.

' M.w.: about 30.000

I The back face of the resultant film was further coated with the following composition which was dried at 120C for 10 minutes to form a surface layer of a film thickness of 0.2 p. to provide film R.

Methanol 400g Acetone 300g Water 300g Poly-Z-hydroxyethyl methacrylate* 5g Prepared according to Synthesis Example 1 On .the opposite surface of the back side layer of films Q and R there was provided a silver halide emulsion layer and a gelatin protective coating as in Example 3 to prepare a photosensitive material, which was cut into pieces each having an area of square 3.5 cm on a side.

The rear side and the emulsion-coated side of each pair of films were put together and contacted under a pressing load of 2 Kg, and then stored for 24 hours at 40C under a relative humidity of As in Example 1, the adhesiveness of the back side was evaluated and the results are shown in Table 6.

Table 6 Film Glossy Area I 0 Approx. 40 R do. 5

Requisite Glossy Area Film drying time (min.)

After 3 days storage After 6 days storage -N-l l5 Approx. 5 Approx. l5 N-Z 8 do. 20 do. 70

N-3 4 do. 40 do. P-l l5 0 0 P-2 8 0 Approx. 10 P-3 do. 20

4 Approx. 5

It will be understood from the above data that film R having a backing layer containing a specific polymer according to this invention has a markedly improved anti-sticking property compared to film Q containing no polymer. As is apparent from this example, the advantageous effect of this invention is also attained by admixing the specific polymer with a backing layer of a photosensitive material.

EXAMPLE 7 To l000g of a gelatino silver iodobromide photographic emulsion containing 1.5 mol silver iodide (the emulsion comprised 14% silver halide, 3.8% gelatin and 82.2% water, the silver halide having an average particle size of 1.4 p.) and sensitized with sodium thiosulfate and sodium tetrachloroaurate there were added 44g of a 1% aqueous solution of -methyl-7-hydroxy- Coating solution S 1 Aqueous bone gelatin solution (6.5%)

1000;; Colloidal siclica lg Aqueous saponin solution l00g Aqueous mucochloric acid solution (27: g Coatin solution T queous solution of graft-copolymer of gelatin with Z-hydroxyethyl methacrylate. [prepared according to Synthesis Example 7) (6.5%) l000g Aqueous saponin solution (l0'7r) 100g queous mucochloric acid solution (2%) 2.5g

Each of films S and T were cut into 2 square pieces 4 cm. on a side and stored for 2 days at lC, 90% RH, and then protective layers of the film S samples were contacted with each other and the protective layers of the film T samples were contacted with each other and all samples stored for 2 days at 35C, 90% RH. The films were stripped off and the surfaces observed as in Example 1. The results are given in Table 7. Film T, a photographic material having the surface layer according to this invention, exhibited a remarkably improved resictance to sticking, as compared to comparative photographic material Film S. Further, film T had the changes and modifications can be made therein without departing from the spirit and scope thereof.

' What is claimed is:

l. A photographic silver halide-containing lightsensitive material characterized by having at least one non-photosensitive surface layer containing at least one polymer containing as its recurringunit at least one monoester of an aliphatic polyhydric alcohol with acrylic acid or methacrylic acid.

2. A material as claimed in claim 1 where the polymer is a homopolymer.

3. A material as claimed in claim 1 wherein the polymer is a copolymer.

.4. A material as claimed in claim 1 wherein the polymer is a graft copolymer.

5. A. material as claimed in claim 2 where the molecular weight of the homopolymer is greater than 10,000.

6. A material as claimed in claim 3 wherein the molecular weight of the copolymer is greater than 10,000.

7. A material as claimed in claim 3 wherein the proportion of the monomethacrylate and/or monoacrylate of the aliphatic polyhydric alcohol in the copolymer is in an excess of mol 8. A material as claimed in claim'4 wherein the graft copolymer comprises from about-5-to about 95% by weight of monomer grafted onto a parent polymer, the monomer comprising at least 50%by weight of mono methacrylate and/or monoacrylate of the aliphatic pol- Table 7 Film Glossy Area (71) S Approx. 85 'l' Approx. 30

yhydric alcohol and the ester being contained in an amount of at least 5% by. weight.

9. A material as claimed in claim 1 wherein the nonphotosensitive surface layer consists essentially of said at least one polymer.

10. A material as claimed in claim 1 wherein the nonphotosensitive surface layer comprises said at least one polymer plus a different polymer.

11. A material as claimed in claim 10 wherein the non-photosensitive surface layer comprises at least 10% by weight of said at least one polymer.

12. A material as claimed in claim 11 wherein said non-photosensitive surface comprises at least 20% of said at least one polymer.

13. A material as claimed in claim 1 wherein the thickness of said non-photosensitive surface layer is at least about 0.3 microns.

14. A material as claimed in claim 13 wherein the thickness of said non-photosensitive surface layer is from 0.5 to 3 microns. v

15. A material as claimed in claim 3 wherein the copolymer is with an olefinic polymerizable monomer.

16. A material as claimed in claim 15 wherein said olefinic polymerizable monomer is a vinylic monomer or a diolefinic' monomer.

17. A material as claimed in claim 1 wherein said ester is selected from the group consisting of 2- hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, S-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaer thritol monomethacrylate, Z-hydroxyethyl acrylate, 3- ydroxypropyl acrylate, 2- hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5- hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate,.diethylene glycol monoacrylate, trimethylolpropane monoacrylate and pentaerythritol monoacrylate. 

1. A PHOTOGRAPHIC SILVER HALIDE-CONTAINING LIGHT-SENSITIVE MATERIAL CHARACTERIZED BY HAVING AT LTEAST ONE NONPHOTOSENSITIVE SURFACE LAYER CONTAINING AT LEAST ONE POLYMER CONTAINING AS ITS RECURRING UNIT AT LEAST ONE MONOESTER OF AN ALIPHATIC POLYHYDRIC ALCOHOL WITH ACRYLIC ACID OR METHACRYLIC ACID.
 2. A material as claimed in claim 1 where the polymer is a homopolymer.
 3. A material as claimed in claim 1 wherein the polymer is a copolymer.
 4. A material as claimed in claim 1 wherein the polymer is a graft copolymer.
 5. A material as claimed in claim 2 where the molecular weight of the homopolymer is greater than 10,000.
 6. A material as claimed in claim 3 wherein the molecular weight of the copolymer is greater than 10,000.
 7. A material as claimed in claim 3 wherein the proportion of the monomethacrylate and/or monoacrylate of the aliphatic polyhydric alcohol in the copolymer is in an excess of 50 mol %.
 8. A material as claimed in claim 4 wherein the graft copolymer comprises from about 5 to about 95% by weight of monomer grafted onto a parent polymer, the monomer comprising at least 50% By weight of monomethacrylate and/or monoacrylate of the aliphatic polyhydric alcohol and the ester being contained in an amount of at least 5% by weight.
 9. A material as claimed in claim 1 wherein the non-photosensitive surface layer consists essentially of said at least one polymer.
 10. A material as claimed in claim 1 wherein the non-photosensitive surface layer comprises said at least one polymer plus a different polymer.
 11. A material as claimed in claim 10 wherein the non-photosensitive surface layer comprises at least 10% by weight of said at least one polymer.
 12. A material as claimed in claim 11 wherein said non-photosensitive surface comprises at least 20% of said at least one polymer.
 13. A material as claimed in claim 1 wherein the thickness of said non-photosensitive surface layer is at least about 0.3 microns.
 14. A material as claimed in claim 13 wherein the thickness of said non-photosensitive surface layer is from 0.5 to 3 microns.
 15. A material as claimed in claim 3 wherein the copolymer is with an olefinic polymerizable monomer.
 16. A material as claimed in claim 15 wherein said olefinic polymerizable monomer is a vinylic monomer or a diolefinic monomer.
 17. A material as claimed in claim 1 wherein said ester is selected from the group consisting of 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate and pentaerythritol monoacrylate. 